Amphiphilic graft copolymers and medical devices with enhanced bond strength

Abstract

Amphiphilic graft copolymers comprise a polypropylene backbone and hybrid micromolecule side-chains based on organo-functional silanes (PP-g-XSiOA) in the presence of a co-agent, for example, difunctional metallic diacrylate monomers, where “X” is an organic group or an organo-functional group, and “A” is a metal, an inorganic oxide, an inorganic hydroxide, or any other inorganic material. X may be derived from a compound selected from the group consisting of epoxy, amino, acrylate, methacryloxy, and vinyl; and A is selected from the group consisting of: silicon, (Si), aluminum (Al), iron (Fe), titanium (Ti), silver (Ag), zinc (Zn), nickel (Ni), calcium (Ca), copper (Cu), tin (Sn); oxides thereof; hydroxides thereof; and mixtures of the foregoing. These copolymers are suitable for forming medical devices and/or as additives to base polymeric formulations for medical devices for improving laser marking, antimicrobial resistance, adhesive free bond strength, paintability and dyeability.

What is claimed is: 
     
       1. An amphiphilic copolymer comprising a polypropylene backbone and an inorganic-organic hybrid side-chain grafted to the polypropylene backbone, the amphiphilic copolymer, which is according to Formula (I): 
       
         
           
           
               
               
           
         
         wherein X is an organic or an organo-functional group containing 1 to 6 carbons; A is selected from the group consisting of: silicon (Si), aluminum (Al), iron (Fe), titanium (Ti), silver (Ag), zinc (Zn), nickel (Ni), calcium (Ca), copper (Cu), tin (Sn), oxides thereof, hydroxides thereof, and mixtures of the foregoing; and n is in the range of about 78 to 99.9 mole percent; m is in the range of about 0.1 to 20 mole percent; the molar value of “y” is in the range of about 0 to 2.0 mole percent; and “Z”, when y is greater than 0, comprises: —X 2 -M; —XSi(OR) 2 ; or —XSi(OH) 3 , wherein “-M-X 2 ” is an organo-metal salt and M is a metal selected from the group consisting of Na, Ca, Mg, Zn, Al and Fe (III) and X 2  is derived from a compound selected from the group consisting of: epoxy, amino, acrylate, methacryloxy, and vinyl, and “OR” is an alkoxy group having 1 to 4 carbons; and 
         the amphiphilic copolymer has a long chain branching frequency in the range of 0.007 to 0.017 per 1000 carbon. 
       
     
     
       2. The amphiphilic copolymer of  claim 1 , wherein the inorganic-organic hybrid side-chain is a reaction product of an organo-silane and an inorganic oxide and/or hydroxide. 
     
     
       3. The amphiphilic copolymer of  claim 1 , wherein X is derived from a compound selected from the group consisting of epoxy, amino, acrylate, methacryloxy, and vinyl; and A is silica or aluminum oxyhydroxide. 
     
     
       4. The amphiphilic copolymer of  claim 1 , wherein the inorganic-organic hybrid side-chain is a reaction product of an organo-functional silane and an inorganic oxide and/or hydroxide in solution, wherein a weight ratio of the organo-functional silane to the inorganic oxide and/or hydroxide is at least 10:1. 
     
     
       5. The amphiphilic copolymer of  claim 1 , wherein y is 0, and the amphiphilic copolymer is according to Formula (IA): 
       
         
           
           
               
               
           
         
       
     
     
       6. The amphiphilic copolymer of  claim 5 , wherein —XSi(OH) 2 O is derived from 3-(trimethoxysilyl)propyl methacrylate. 
     
     
       7. The amphiphilic copolymer of  claim 6 , wherein A is derived from Si(OH) 4  or SiO 2 . 
     
     
       8. The amphiphilic copolymer of  claim 1  having a melting point in the range of 140 to 180° C. 
     
     
       9. The amphiphilic copolymer of  claim 1  having a capillary viscosity in the range of 100 to 300 Pa·s at 180 s −1 . 
     
     
       10. The amphiphilic copolymer of  claim 1  having a weight average molecular weight (Mw) in the range of about 100,000 to about 350,000 g/mol. 
     
     
       11. The amphiphilic copolymer of  claim 1  having a dispersity index in the range of 1.5 to 9. 
     
     
       12. The amphiphilic copolymer of  claim 1  having a melt flow rate in the range of 15 to 55 g/10 minutes. 
     
     
       13. A medical device formed from a blend comprising:
 a base polymeric formulation comprising at least a homopolymer or co-polymer of propylene; and 
 an additive comprising a copolymer (PP-g-XSiOA) comprising a polypropylene backbone and an inorganic-organic hybrid side-chain grafted to the polypropylene backbone, the amphiphilic copolymer, which is according to Formula (I): 
 
       
         
           
           
               
               
           
         
         where “X” is an organic group or an organo-functional group containing 1 to 6 carbons; “A” is selected from the group consisting of: silicon (Si), aluminum (Al), iron (Fe), titanium (Ti), silver (Ag), zinc (Zn), nickel (Ni), calcium (Ca), copper (Cu), tin (Sn), oxides thereof, hydroxides thereof, and mixtures of the foregoing; and n is in the range of about 78 to 99.9 mole percent; m is in the range of about 0.1 to 20 mole percent; the molar value of “y” is in the range of about 0 to 2.0 mole percent; and “Z”, when y is greater than 0, comprises: —X 2 -M; —XSi(OR) 3 ; or —XSi(OH) 3 , wherein “-M-X 2 ” is an organo-metal salt and M is a metal selected from the group consisting of Na, Ca, Mg, Zn, Al and Fe (III) and X 2  is derived from a compound selected from the group consisting of: epoxy, amino, acrylate, methacryloxy, and vinyl, and “OR” is an alkoxy group having 1 to 4 carbons; and 
         wherein the copolymer (PP-g-XSiOA) has a long chain branching frequency in the range of 0.007 to 0.017 per 1000 carbon; 
         the PP-g-XSiOA being present in the blend in a range of about 0.01 to about 20.0% by weight of the blend. 
       
     
     
       14. The medical device of  claim 13 , wherein the base polymeric formulation comprises polypropylene homopolymer, a polyethylene-polypropylene co-polymer, a polypropylene-containing thermoplastic elastomer (TPE), or combinations thereof. 
     
     
       15. The medical device of  claim 13 , wherein X of the PP-g-XSiOA is derived from a compound selected from the group consisting of epoxy, amino, acrylate, methacryloxy, and vinyl; and A is silica or aluminum oxyhydroxide. 
     
     
       16. The medical device of  claim 13 , which has one or more improved characteristics relative to a comparative base polymeric formulation comprising at least a homopolymer or co-polymer of propylene without a PP-g-XSiOA additive, the improved characteristic being selected from the group consisting of: laser printability and/or marking; solvent bonding, and melt adhesion to polar surfaces. 
     
     
       17. The medical device of  claim 13  which is in the form of tubing. 
     
     
       18. A medical device comprising:
 a tubing comprising a polymeric blend comprising a base polymeric formulation comprising at least a homopolymer or co-polymer of propylene, and an additive comprising a copolymer (PP-g-XSiOA) comprising a polypropylene backbone and an inorganic-organic hybrid side-chain grafted to the polypropylene backbone, the amphiphilic copolymer, which is according to Formula (I): 
 
       
         
           
           
               
               
           
         
         where “X” is an organic group or an organo-functional group containing 1 to 6 carbons; “A” is selected from the group consisting of: silicon (Si), aluminum (Al), iron (Fe), titanium (Ti), silver (Ag), zinc (Zn), nickel (Ni), calcium (Ca), copper (Cu), tin (Sn), oxides thereof, hydroxides thereof, and mixtures of the foregoing; and n is in the range of about 78 to 99.9 mole percent; m is in the range of about 0.1 to 20 mole percent; the molar value of “y” is in the range of about 0 to 2.0 mole percent; and “Z”, when y is greater than 0, comprises: —X 2 -M; —XSi(OR) 3 ; or —XSi(OH) 3 , wherein “-M-X 2 ” is an organo-metal salt and M is a metal selected from the group consisting of Na, Ca, Mg, Zn, Al and Fe (III) and X 2  is derived from a compound selected from the group consisting of: epoxy, amino, acrylate, methacryloxy, and vinyl, and “OR” is an alkoxy group having 1 to 4 carbons; and wherein the copolymer (PP-g-XSiOA) has a long chain branching frequency in the range of 0.007 to 0.017 per 1000 carbon;
 wherein the PP-g-XSiOA is present in the blend in an amount in the range of about 0.01 to about 20.0% by weight of the blend; and 
 
         a connector bonded to the tubing. 
       
     
     
       19. The medical device of  claim 18 , wherein the base polymeric formulation comprises polypropylene homopolymer, a polyethylene-polypropylene co-polymer, a polypropylene-containing thermoplastic elastomer (TPE), or combinations thereof. 
     
     
       20. The medical device of  claim 18 , wherein X of the PP-g-XSiOA is derived from a compound selected from the group consisting of epoxy, amino, acrylate, methacryloxy, and vinyl; and A is silica or aluminum oxyhydroxide. 
     
     
       21. The medical device of  claim 18 , wherein the connector comprises a metal. 
     
     
       22. The medical device of  claim 21 , wherein the metal is selected from the group consisting of: steel, cobalt, titanium, tantalum, and their alloys. 
     
     
       23. The medical device of  claim 21 , wherein the connector is melt-bonded to the tubing. 
     
     
       24. The medical device of  claim 18 , wherein the connector comprises a polar material. 
     
     
       25. The medical device of  claim 24 , wherein the polar material is selected from the group consisting of: poly(methyl methacrylate) (PMMA), styrene maleic anhydride (SMA), polycarbonate (PC), and methyl methacrylate-acrylonitrile-butadiene-styrene (MABS). 
     
     
       26. The medical device of  claim 24 , wherein the connector is solvent-bonded to the tubing. 
     
     
       27. A method of making a medical device comprising:
 obtaining a copolymer (PP-g-XSiOA) comprising a polypropylene backbone and an inorganic-organic hybrid side-chain grafted to the polypropylene backbone, the amphiphilic copolymer, which is according to Formula (I): 
 
       
         
           
           
               
               
           
         
         where “X” is an organic group or an organo-functional group containing 1 to 6 carbons; “A” is selected from the group consisting of: silicon (Si), aluminum (Al), iron (Fe), titanium (Ti), silver (Ag), zinc (Zn), nickel (Ni), calcium (Ca), copper (Cu), tin (Sn), oxides thereof, hydroxides thereof, and mixtures of the foregoing; and “Z”, when y is greater than 0, comprises: —X 2 -M; —XSi(OR) 3 ; or —XSi(OH) 3 , wherein “-M-X 2 ” is an organo-metal salt and M is a metal selected from the group consisting of Na, Ca, Mg, Zn, Al and Fe (III) and X 2  is derived from a compound selected from the group consisting of: epoxy, amino, acrylate, methacryloxy, and vinyl, and “OR” is an alkoxy group having 1 to 4 carbons; and wherein the copolymer (PP-g-XSiOA) has a long chain branching frequency in the range of 0.007 to 0.017 per 1000 carbon; 
         combining the PP-g-XSiOA with a base polymeric formulation comprising at least a homopolymer or co-polymer of propylene to form a blend, the PP-g-XSiOA being present in the blend in a range of about 0.01 to about 20.0% by weight of the blend; 
         forming a tubing from the blend; and 
         bonding the tubing to a connector in the absence of an adhesive to form the medical device. 
       
     
     
       28. The method of  claim 27 , wherein the connector comprises a metal. 
     
     
       29. The method of  claim 28 , wherein the metal is selected from the group consisting of: steel, cobalt, titanium, tantalum, and their alloys. 
     
     
       30. The method of  claim 28 , wherein the connector is melt-bonded to the tubing. 
     
     
       31. The method of  claim 27 , wherein the connector comprises a polar material. 
     
     
       32. The method of  claim 31 , wherein the polar material is selected from the group consisting of: poly(methyl methacrylate) (PMMA), styrene maleic anhydride (SMA), polycarbonate (PC), and methyl methacrylate-acrylonitrile-butadiene-styrene (MABS). 
     
     
       33. The method of  claim 31 , wherein the connector is solvent-bonded to the tubing.